Real-Space Bonding Indicator Analysis of the Donor–Acceptor Complexes X₃BNY₃, X₃AlNY₃, X₃BPY₃, and X₃AlPY₃ (X, Y = H, Me, Cl)

Calculations of real-space bonding indicators (RSBI) derived from Atoms-In-Molecules (AIM), Electron Localizability Indicator (ELI-D), Non-Covalent Interactions index (NCI), and Density Overlap Regions Indicator (DORI) toolkits for a set of 36 donor–acceptor complexes X₃BNY₃ (<b>1</b>, <b>1a</b>–<b>1h</b>), X₃AlNY₃ (<b>2</b>, <b>2a</b>–<b>2h</b>), X₃BPY₃ (<b>3</b>, <b>3a</b>–<b>3h</b>), and X₃AlPY₃ (<b>4</b>, <b>4a</b>–<b>4h</b>) reveal that the donor–acceptor bonds comprise covalent and ionic interactions in varying extents (X = Y = H for <b>1</b>–<b>4</b>; X = H, Y = Me for <b>1a</b>–<b>4a</b>; X = H, Y = Cl for <b>1b</b>–<b>4b</b>; X = Me, Y = H for <b>1c</b>–<b>4c</b>; X, Y = Me for <b>1d</b>–<b>4d</b>; X = Me, Y = Cl for <b>1e</b>–<b>4e</b>; X = Cl, Y = H for <b>1f</b>–<b>4f</b>; X = Cl, Y = Me for <b>1g</b>–<b>4g</b>; X, Y = Cl for <b>1h</b>–<b>4h</b>). The phosphinoboranes X₃BPY₃ (<b>3</b>, <b>3a</b>–<b>3h</b>) in general and Cl₃BPMe₃ (<b>3f</b>) in particular show the largest covalent contributions and the least ionic contributions. The aminoalanes X₃AlNY₃ (<b>2</b>, <b>2a</b>–<b>2h</b>) in general and Me₃AlNCl₃ (<b>2e</b>) in particular show the least covalent contributions and the largest ionic contributions. The aminoboranes X₃BNY₃ (<b>1</b>, <b>1a</b>–<b>1h</b>) and the phosphinoalanes X₃AlPY₃ (<b>4</b>, <b>4a</b>–<b>4h</b>) are midway between phosphinoboranes and aminoalanes. The degree of covalency and ionicity correlates with the electronegativity difference BP (<i>ΔEN</i> = 0.15) < AlP (<i><i>ΔEN</i></i> = 0.58) < BN (ΔEN = 1.00) < AlN (<i>ΔEN</i> = 1.43) and a previously published energy decomposition analysis (EDA). To illustrate the importance of both contributions in Lewis formula representations, two resonance formulas should be given for all compounds, namely, the canonical form with formal charges denoting covalency and the arrow notation pointing from the donor to the acceptor atom to emphasis ionicity. If the Lewis formula mainly serves to show the atomic connectivity, the most significant should be shown. Thus, it is legitimate to present aminoalanes using arrows; however, for phosphinoboranes the canonical form with formal charges is more appropriate

Real-Space Bonding Indicator Analysis of the Donor–Acceptor Complexes X₃BNY₃, X₃AlNY₃, X₃BPY₃, and X₃AlPY₃ (X, Y = H, Me, Cl)

Calculations of real-space bonding indicators (RSBI) derived from Atoms-In-Molecules (AIM), Electron Localizability Indicator (ELI-D), Non-Covalent Interactions index (NCI), and Density Overlap Regions Indicator (DORI) toolkits for a set of 36 donor–acceptor complexes X₃BNY₃ (<b>1</b>, <b>1a</b>–<b>1h</b>), X₃AlNY₃ (<b>2</b>, <b>2a</b>–<b>2h</b>), X₃BPY₃ (<b>3</b>, <b>3a</b>–<b>3h</b>), and X₃AlPY₃ (<b>4</b>, <b>4a</b>–<b>4h</b>) reveal that the donor–acceptor bonds comprise covalent and ionic interactions in varying extents (X = Y = H for <b>1</b>–<b>4</b>; X = H, Y = Me for <b>1a</b>–<b>4a</b>; X = H, Y = Cl for <b>1b</b>–<b>4b</b>; X = Me, Y = H for <b>1c</b>–<b>4c</b>; X, Y = Me for <b>1d</b>–<b>4d</b>; X = Me, Y = Cl for <b>1e</b>–<b>4e</b>; X = Cl, Y = H for <b>1f</b>–<b>4f</b>; X = Cl, Y = Me for <b>1g</b>–<b>4g</b>; X, Y = Cl for <b>1h</b>–<b>4h</b>). The phosphinoboranes X₃BPY₃ (<b>3</b>, <b>3a</b>–<b>3h</b>) in general and Cl₃BPMe₃ (<b>3f</b>) in particular show the largest covalent contributions and the least ionic contributions. The aminoalanes X₃AlNY₃ (<b>2</b>, <b>2a</b>–<b>2h</b>) in general and Me₃AlNCl₃ (<b>2e</b>) in particular show the least covalent contributions and the largest ionic contributions. The aminoboranes X₃BNY₃ (<b>1</b>, <b>1a</b>–<b>1h</b>) and the phosphinoalanes X₃AlPY₃ (<b>4</b>, <b>4a</b>–<b>4h</b>) are midway between phosphinoboranes and aminoalanes. The degree of covalency and ionicity correlates with the electronegativity difference BP (<i>ΔEN</i> = 0.15) < AlP (<i><i>ΔEN</i></i> = 0.58) < BN (ΔEN = 1.00) < AlN (<i>ΔEN</i> = 1.43) and a previously published energy decomposition analysis (EDA). To illustrate the importance of both contributions in Lewis formula representations, two resonance formulas should be given for all compounds, namely, the canonical form with formal charges denoting covalency and the arrow notation pointing from the donor to the acceptor atom to emphasis ionicity. If the Lewis formula mainly serves to show the atomic connectivity, the most significant should be shown. Thus, it is legitimate to present aminoalanes using arrows; however, for phosphinoboranes the canonical form with formal charges is more appropriate

Bis(<i>m</i>‑terphenyl)silanes

The synthesis and full characterization of the first bis­(<i>m</i>-terphenyl)­silanes, namely, (2,6-Mes₂C₆H₃)₂SiF₂, (2,6-Mes₂C₆H₃)₂SiHF, and (2,6-Mes₂C₆H₃)₂SiH₂, is reported

Concomitant Reactivity of the <i>m</i>-Terphenylindium Dihydroxide [2,6-Mes₂C₆H₃In(OH)₂]₄ toward Carbon Dioxide and Ethylene Glycol

The stepwise reaction of [2,6-Mes₂C₆H₃In­(OH)₂]₄ with carbon dioxide and ethylene glycol proceeded with the formation of (2,6-Mes₂C₆H₃In)₄­(CO₃)₂(OH)₄(H₂O)₂ (<b>1</b>) and (2,6-Mes₂C₆H₃In)₄(OCH₂CH₂O)₂(OH)₄ (<b>2</b>), respectively, and eventually produced (2,6-Mes₂C₆H₃In)₄(CO₃)₂­(OCH₂CH₂OH)₂(OH)₂ (<b>3</b>). Attempts to liberate ethylene carbonate upon heating of <b>3</b> were unsuccessful

Synthesis and Structure of an Intramolecularly Coordinated Diaryltelluronic Acid and Its Dimethyl Ester

The oxidation of the telluroxane cluster (8-Me₂NC₁₀H₆Te)₆O₈(OH)₂ (<b>4</b>) or the diaryl ditelluride (8-Me₂NC₁₀H₆Te)₂ (<b>7</b>) using H₂O₂ provided the diarylditelluronic acid [8-Me₂NC₁₀H₆Te­(O)­(OH)₂]₂(O) (<b>6</b>), which is the second member of this compound class and the first one to contain an intramolecularly coordinated substituent. Attempts at recrystallizing <b>6</b> from Methanol provided the partial ester [8-Me₂NC₁₀H₆Te­(O)­(OH)­(OMe)]₂(O) (<b>8</b>). In addition structural motifs of known diaryltelluronic acids were compared using DFT calculations

Polyfluorinated Functionalized <i>m</i>‑Terphenyls. New Substituents and Ligands in Organometallic Synthesis

The synthesis and structural characterization of polyfluorinated arenes 2,4,6-(C₆F₅)₃C₆H₂X and 2,6-(C₆F₅)₂-4-BrC₆H₂X (X = NO₂, Cl, Br) obtained in the Ullmann-type cross coupling reaction is reported. The nitro derivatives were reduced to the aromatic amines. The α-diimine [2,4,6-(C₆F₅)₃C₆H₂NCMe]₂ and 2,4,6-(C₆F₅)₃C₆H₂I were obtained in condensation and Sandmeyer reactions, respectively, from the corresponding amine. The syntheses of 2,4,6-(C₆F₅)₃C₆H₂NHC­(O)­H, 2,4,6-(C₆F₅)₃C₆H₂NC, and 2,4,6-(C₆F₅)₃C₆H₂Si­(X)­Me₂ (X = H, F, Cl) are also described

Concomitant Reactivity of the <i>m</i>-Terphenylindium Dihydroxide [2,6-Mes₂C₆H₃In(OH)₂]₄ toward Carbon Dioxide and Ethylene Glycol

The stepwise reaction of [2,6-Mes₂C₆H₃In­(OH)₂]₄ with carbon dioxide and ethylene glycol proceeded with the formation of (2,6-Mes₂C₆H₃In)₄­(CO₃)₂(OH)₄(H₂O)₂ (<b>1</b>) and (2,6-Mes₂C₆H₃In)₄(OCH₂CH₂O)₂(OH)₄ (<b>2</b>), respectively, and eventually produced (2,6-Mes₂C₆H₃In)₄(CO₃)₂­(OCH₂CH₂OH)₂(OH)₂ (<b>3</b>). Attempts to liberate ethylene carbonate upon heating of <b>3</b> were unsuccessful

Concomitant Reactivity of the <i>m</i>-Terphenylindium Dihydroxide [2,6-Mes₂C₆H₃In(OH)₂]₄ toward Carbon Dioxide and Ethylene Glycol

The stepwise reaction of [2,6-Mes₂C₆H₃In­(OH)₂]₄ with carbon dioxide and ethylene glycol proceeded with the formation of (2,6-Mes₂C₆H₃In)₄­(CO₃)₂(OH)₄(H₂O)₂ (<b>1</b>) and (2,6-Mes₂C₆H₃In)₄(OCH₂CH₂O)₂(OH)₄ (<b>2</b>), respectively, and eventually produced (2,6-Mes₂C₆H₃In)₄(CO₃)₂­(OCH₂CH₂OH)₂(OH)₂ (<b>3</b>). Attempts to liberate ethylene carbonate upon heating of <b>3</b> were unsuccessful

Intramolecularly Coordinated (6-(Diphenylphosphino)acenaphth-5-yl)stannanes. Repulsion vs Attraction of P- and Sn-Containing Substituents in the <i>peri</i> Positions

The intramolecularly coordinated (6-(diphenylphosphino)­acenaphth-5-yl)­stannanes ArSnBu₃ (<b>1</b>), ArSnPh₃ (<b>2</b>), ArSnPh₂Cl (<b>3</b>), ArSnPhCl₂ (<b>4</b>), ArSnCl₃ (<b>5</b>), Ar₂SnCl₂ (<b>6</b>), ArSnPh₂O₃SCF₃ (<b>7</b>), and ArSnPh₂F (<b>8</b>) were synthesized and fully characterized by multinuclear NMR spectroscopy (¹¹⁹Sn, ³¹P, ¹⁹F, ¹³C, ¹H) and X-ray crystallography (Ar = 6-Ph₂P-Ace-5-). Due to the different substituents, the Lewis acidities of the Sn atoms of <b>1</b>–<b>8</b> vary substantially, which is reflected in the different P–Sn <i>peri</i> distances lying in the range from 2.7032(9) to 3.332(2) Å. In MeCN, <b>7</b> undergoes electrolytic dissociation into solvated triarylstannyl cations and triflate anions. The gas-phase structures of <b>2</b>–<b>5</b>, <b>8</b>, and the triarylstannyl cations ArPh₂Sn⁺ (<b>7a</b>) and [ArPh₂Sn·NCMe]⁺ (<b>7b</b>) were obtained by geometry optimization at the B3PW91/TZ level of theory. A detailed analysis of a set of real-space bonding indicators (RSBI) derived from the electron and pair densities following the atoms in molecules (AIM) and electron localizability indicator (ELI-D) topological approaches, respectively, uncovers the Sn–P <i>peri</i> interaction in <b>2</b> to be in the border regime between nonbonding and weakly ionic. With an increasing number of Cl atoms attached to the Sn atom, the Sn–P bond becomes considerably shorter and exhibits a decreasingly polar covalent interaction. As expected, this trend is significantly enhanced for the Sn–P interactions in the charged compounds <b>7a</b>,<b>b</b>. The Sn–P bond properties of <b>8</b>, however, very much resemble those of <b>3</b>, which means that the electronic impact of the F atom in the axial position is comparable to that of the axial Cl atom

<i>Peri</i>-Substituted (Ace)Naphthylphosphinoboranes. (Frustrated) Lewis Pairs

The synthesis and molecular structures of 1-(diphenylphosphino)-8-naphthyldimesitylborane (<b>1</b>) and 5-(diphenylphosphino)-6-acenaphthyldimesitylborane (<b>2</b>) are reported. The experimentally determined P–B <i>peri</i> distances of 2.162(2) and 3.050(3) Å allow <b>1</b> and <b>2</b> to be classified as regular and frustrated Lewis pairs. The electronic characteristics of the (non)­bonding P–B contacts are determined by analysis of a set of real-space bonding indicators (RSBIs) derived from the theoretically calculated electron and pair densities. These densities are analyzed utilizing the atoms-in-molecules (AIM), stockholder, and electron-localizability-indicator (ELI-D) space partitioning schemes. The recently introduced mapping of the electron localizability on the ELI-D basin surfaces is also applied. All RSBIs clearly discriminate the bonding P–B contact in <b>1</b> from the nonbonding P–B contact in <b>2</b>, which is due to the fact that the acenaphthene framework is rather rigid, whereas the naphthyl framework shows sufficient conformational flexibility, allowing shorter <i>peri</i> interations. The results are compared to the previously known prototypical phosphinoborane Ph₃PB­(C₆F₅)₃, which serves as a reference for a bonding P–B interaction. The most prominent features of the nonbonding P–B contact in <b>2</b> are the lack of an AIM bond critical point, the unaffected Hirshfeld surfaces of the P and B atomic fragments, and the negligible penetration of the electron population of the ELI-D lone pair basin of the P atom into the AIM B atomic basin